The coordination of β-amino ketoximes with divalent iron, cobalt, nickel and zinc

Abstract

The iron(II), nickel(II) and zinc(II) complexes of the diamine dioxime ligand 4,4,9,9-tetramethyl-5,8-diazadodecane-2,11-dione dioxime (H₂dddo) and the cobalt(II), nickel(II) and zinc(II) complexes of its O-methyl ether (Hddmo) have been studied potentiometrically at 25°C, I 0.10M NaCl. Stability constant data are compared with those obtained for the copper(II) and cobalt(II) complexes of H₂dddo and the copper(II) complexes of Hddmo. H₂dddo coordinates in the oxime-oximato form [M(Hdddo)]⁺ with iron(II), cobalt(II), nickel(II) and zinc(II) Hddmo forms complexes with the ligand coordinated in the oxime form [M(Hddmo)]²⁺ and the oximato form [M(ddmo)]⁺. The complexes [Zn(Hddmo)₂]²⁺, [Zn(Hddmo)(ddmo)]⁺ and [Co(ddmo)(OH)] were also characterized in aqueous solution. The stability order Fe^II < Co^II < Ni^II < Cu^II > Zn^II was observed for the formation of 1 : 1 complexes with the ligands Hdddo- (log K = 8.8, 11.7, 15.2, 23.3, 12.0 for Fe to Zn respectively) and Hddmo (5.7, 6.6, 12.1, 5.3 for Co to Zn). The infrared spectra of the complexes [Ni(Hdddo)] ClO₄,H₂O and [Zn(Hdddo)] ClO₄ are discussed in terms of oxime-oximato hydrogen bonding.